JP4873726B2 - Method for forming zinc oxide thin film - Google Patents
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- JP4873726B2 JP4873726B2 JP2007080250A JP2007080250A JP4873726B2 JP 4873726 B2 JP4873726 B2 JP 4873726B2 JP 2007080250 A JP2007080250 A JP 2007080250A JP 2007080250 A JP2007080250 A JP 2007080250A JP 4873726 B2 JP4873726 B2 JP 4873726B2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims description 68
- 239000010409 thin film Substances 0.000 title claims description 36
- 239000011787 zinc oxide Substances 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 17
- 239000007789 gas Substances 0.000 claims description 68
- 239000000758 substrate Substances 0.000 claims description 56
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000012159 carrier gas Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 4
- 230000001603 reducing effect Effects 0.000 claims description 4
- 125000002524 organometallic group Chemical group 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 238000002128 reflection high energy electron diffraction Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- QQTGJVBUIOTPGZ-UHFFFAOYSA-N CCC[Zn]CCC Chemical compound CCC[Zn]CCC QQTGJVBUIOTPGZ-UHFFFAOYSA-N 0.000 description 1
- FPAYFBDVIZFSFJ-UHFFFAOYSA-N CC[Zn]C Chemical compound CC[Zn]C FPAYFBDVIZFSFJ-UHFFFAOYSA-N 0.000 description 1
- 238000005162 X-ray Laue diffraction Methods 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- -1 pressure Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
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- Chemical Vapour Deposition (AREA)
Description
本発明は、ＺｎＯ−ＬＥＤ材料等として有用な有機金属堆積法（ＭＯＣＶＤ）による酸化亜鉛薄膜の新しい形成方法に関するものである。 The present invention relates to a new method for forming a zinc oxide thin film by metal organic deposition (MOCVD) useful as a ZnO-LED material or the like.
酸化亜鉛（ＺｎＯ）は、３．３ｅＶのバンドギャップと６０ｍｅＶのエキシトンの結合エネルギーを持つために、室温で効率的な紫外線発生デバイス（ＬＥＤ）材料として有望であることが知られている。また、ＺｎＯ−ＬＥＤの実用化に向けての有力な酸化亜鉛薄膜の形成方法の一つとして有機金属堆積法（ＭＯＣＶＤ）が考慮されている。 Zinc oxide (ZnO) has a band gap of 3.3 eV and an exciton binding energy of 60 meV, and is known to be promising as an efficient ultraviolet light generating device (LED) material at room temperature. In addition, metal organic deposition (MOCVD) is considered as one of the effective methods for forming a zinc oxide thin film for practical application of ZnO-LEDs.
しかしながら、このＭＯＣＶＤによるＺｎＯ薄膜の成長においては柱状成長しやすく、表面が平坦なものを得ることが難しいという問題点がある。実際、II族源としてのジエチル亜鉛（ＤＥＺｎ）有機金属ガスとVI族源としての酸素ガスを利用したＭＯＣＶＤによるＺｎＯ（II−VI族化合物半導体）薄膜では、通常、ナノカラムやウイスカーが成長しやすく、表面が平坦なＺｎＯ薄膜を得ることは難しい。 However, the growth of ZnO thin films by MOCVD has a problem that columnar growth is easy and it is difficult to obtain a flat surface. In fact, in ZnO (II-VI group compound semiconductor) thin film by MOCVD using diethyl zinc (DEZn) organometallic gas as group II source and oxygen gas as group VI source, nanocolumns and whiskers are usually easy to grow, It is difficult to obtain a ZnO thin film having a flat surface.
そこで、Ｚｎの供給源として、酸素に対して安定なＺｎ（ａｃａｃ）2やＺｎ（ｄｐｍ
）2などの有機金属ガスを用いることや、VI族源としてＨ2Ｏ、ｔ−ＢｕＯＨ（ターシャリーブタノール）、ｉ−ＰｒＯＨ（イソプロパノール）などの還元的性質を持つガスを原料とするＭＯＣＶＤ−ＺｎＯ薄膜の成長が試みられてきた（たとえば非特許文献１−２参照）が、それでも原子レベルで平坦で高品質なＺｎＯ薄膜を得ることは困難であった。
2 ) MOCVD-ZnO using a metal having a reducing property such as H 2 O, t-BuOH (tertiary butanol), i-PrOH (isopropanol) as a group VI source Although attempts have been made to grow a thin film (see, for example, Non-Patent Document 1-2), it is still difficult to obtain a ZnO thin film that is flat at the atomic level and has high quality.
本願発明は、以上のとおりの背景から、従来技術の問題点を解消して、表面が平坦な、エピタキシャルなＺｎＯ薄膜をＭＯＣＶＤにより成長させることのできる新しい方法を提供することを課題としている。 The present invention has an object to solve the problems of the prior art and provide a new method by which an epitaxial ZnO thin film having a flat surface can be grown by MOCVD from the background as described above.
本発明は、上記の課題を解決するものとして、以下のことを特徴としている。 The present invention is characterized by the following in order to solve the above problems.
第１：ジアルキル亜鉛有機金属ガスと酸素との原料ガスのＭＯＣＶＤ（有機金属堆積法）による酸化亜鉛薄膜の成形方法であって、ジアルキル亜鉛有機金属ガスのキャリアガスを水素含有ガスとし、かつ、水素含有ガスからなる雰囲気形成ガスによって反応域を還元性雰囲気として、かつ、基板近傍において原料ガスと雰囲気形成ガスとが混ざるようにして、基板上に酸化亜鉛薄膜を成長させる。
First: A method of forming a zinc oxide thin film by MOCVD (organometallic deposition) of a source gas of dialkyl zinc organometallic gas and oxygen, wherein the carrier gas of dialkyl zinc organometallic gas is a hydrogen-containing gas, and hydrogen A zinc oxide thin film is grown on the substrate such that the reaction zone is made a reducing atmosphere by the atmosphere forming gas composed of the contained gas , and the source gas and the atmosphere forming gas are mixed in the vicinity of the substrate.
第２：基板上を通過した原料ガスは再度基板まで還流しないようにする。 Second: The source gas that has passed over the substrate is prevented from refluxing again to the substrate.
第３：原料ガスを基板上に供給しながら、基板の加熱温度を変更する。
Third : The substrate heating temperature is changed while supplying the source gas onto the substrate.
第４：原料ガスの基板上への供給とその停止の繰り返しを、基板の加熱温度の
Ｔ１＜Ｔ２
（Ｔ１は原料ガス供給時の温度、Ｔ２は原料ガスの供給停止時の温度）
の変更と連動させる。
Fourth : Repeating the supply of the source gas onto the substrate and the stop thereof, the substrate heating temperature T 1 <T 2
(T 1 is the temperature when the source gas is supplied, and T 2 is the temperature when the supply of the source gas is stopped)
Linked with changes.
第５：レーザー源からのレーザー光の直接的照射により基板を加熱する。
5th : The substrate is heated by direct irradiation of laser light from a laser source.
上記のとおりの本発明の酸化亜鉛薄膜の形成方法によれば、従来方法における柱状成長を抑え、表面が平坦な、エキタキシャルなＺｎＯ薄膜をＭＯＣＶＤにより成長させることができる。この薄膜によって、ＺｎＯ−ＬＥＤ材料としての実用性を大きく前進させることができる。 According to the method for forming a zinc oxide thin film of the present invention as described above, the columnar growth in the conventional method can be suppressed, and an epitaxial ZnO thin film having a flat surface can be grown by MOCVD. This thin film can greatly advance the practicality as a ZnO-LED material.
本発明の特徴は上記のとおりであるが、以下にその実施の形態について説明する。 The features of the present invention are as described above, and the embodiments thereof will be described below.
本発明においては、ＭＯＣＶＤのための原料ガスとしては、一般式がＲ1−Ｚｎ−Ｒ2（Ｒ1およびＲ2は、同一または別異のアルキル基を示す）で表わされるジアルキル亜鉛の有機金属ガスと酸素とを用いるが、この場合のジアルキル亜鉛としては、たとえば代表的なものとしてジエチル亜鉛（ＤＥＺｎ）、ジメチル亜鉛（ＤＭＺｎ）、ジプロピル亜鉛（ＤＰＺｎ）、エチルメチル亜鉛（ＥＭＺｎ）等の低級アルキル（炭素数４以下）基を有する有機亜鉛化合物を例示することができる。 In the present invention, an organic metal of dialkylzinc represented by the general formula R 1 —Zn—R 2 (R 1 and R 2 are the same or different alkyl groups) is used as a source gas for MOCVD. Gas and oxygen are used. In this case, typical examples of dialkylzinc include lower alkyl such as diethylzinc (DEZn), dimethylzinc (DMZn), dipropylzinc (DPZn), and ethylmethylzinc (EMZn). An organic zinc compound having a group having 4 or less carbon atoms can be exemplified.
そして、本発明においては、これらの原料ガスを用いてのＭＯＣＶＤによる酸化亜鉛薄膜の成長に際し、ジアルキル亜鉛有機金属ガスのキャリアガスとして、水素含有ガスを用い、かつ、水素含有ガスからなる雰囲気形成ガスによって反応域を還元性雰囲気とすることを必須としている。また、本発明のＭＯＣＶＤは、これらのガスを固体基板に対してフロー（流れ）状態において実施するとが好ましい。 In the present invention, in the growth of a zinc oxide thin film by MOCVD using these raw material gases, an atmosphere forming gas comprising a hydrogen-containing gas and a hydrogen-containing gas is used as a carrier gas for the dialkyl zinc organometallic gas. Therefore, it is essential to make the reaction zone a reducing atmosphere. Moreover, it is preferable that the MOCVD of the present invention is carried out in a flow state with respect to the solid substrate.
原料ガス、キャリアガス等の供給割合については、一般的には、ジアルキル亜鉛と酸素とのモル比は、
ジアルキル亜鉛／Ｏ2として１／５００〜１／５
とすることが考慮される。また、容量比としては、
ジアルキル亜鉛／Ｏ2＝０．５〜３００
キャリアガス中の水素ガス／ジアルキル亜鉛＝５〜４０
水素ガス（全体）／Ｏ2＝５０〜８０００
の範囲が好適なものとして考慮される。
Regarding the supply ratio of source gas, carrier gas, etc., in general, the molar ratio of dialkylzinc and oxygen is
1/500 to 1/5 as dialkyl zinc / O 2
Is considered. As a capacity ratio,
Dialkyl zinc / O 2 = 0.5 to 300
Hydrogen gas in carrier gas / dialkyl zinc = 5-40
Hydrogen gas (whole) / O 2 = 50 to 8000
Is considered as preferred.
なお、キャリアガス並びに雰囲気形成ガスにおける水素ガスについては、主として水素ガス、つまり５０容量％以上が水素ガスであることが望ましい。５０容量％未満の他の不活性ガス、たとえばＡｒ、Ｈｅ等の希ガスやＮ2等との混合ガスであってもよい。 As for the hydrogen gas in the carrier gas and the atmosphere forming gas, it is desirable that mainly hydrogen gas, that is, 50% by volume or more is hydrogen gas. Other inert gas less than 50% by volume, for example, a rare gas such as Ar or He, or a mixed gas with N 2 or the like may be used.
反応域の圧力は、通常は、０．５〜１００Ｔｏｒｒ、基板温度は３５０℃〜９００℃の範囲が考慮される。なお、基板については各種のものであってよく、たとえば、サファイア、シリコン、石英、ガラス等の各種のものが例示される。また、本発明においては、基板上を通過した原料ガスは再度基板まで還流しないように流通させることが好ましい。そして、基板近傍において原料ガスと雰囲気ガスとが混ざるようにすることが好ましい。これらのための手段は適宜であってよいが、たとえば、後述の実施例にも示したように、ガスの流通空間を介して基板表面を覆うようにしたフローチャンネルを用いて、ガスのフロー状態を、仕切り板によって、（Ａ）ジアルキル亜鉛有機金属ガスとキャリアーガスの水素ガスとの混合ガス、（Ｂ）酸素ガスの順となる２層流、あるいはさらに（Ｃ）水素ガスとの順となる３層流等となるようにすることが考慮される。そして、このガスフローチャンネルでは、基板近傍において原料ガスと雰囲気形成ガスとが混ざるようにし、さらには
、基板上を通過した原料ガスはガスフローチャンネルに沿って排出されて再度基板まで還流しないようにすること等が考慮される。
In general, the pressure in the reaction zone is 0.5 to 100 Torr, and the substrate temperature is 350 ° C. to 900 ° C. The substrate may be various types, and examples thereof include various types such as sapphire, silicon, quartz, and glass. In the present invention, the source gas that has passed over the substrate is preferably circulated so as not to recirculate to the substrate. It is preferable that the source gas and the atmospheric gas are mixed in the vicinity of the substrate. The means for these may be appropriate, for example, as shown in the examples described later, the flow state of the gas using the flow channel that covers the substrate surface through the gas circulation space Are divided into (A) a mixed gas of a dialkyl zinc organometallic gas and a carrier gas hydrogen gas, (B) a two-layer flow in the order of oxygen gas, or (C) a hydrogen gas in that order. Considering a three-layer flow or the like. In this gas flow channel, the source gas and the atmosphere forming gas are mixed in the vicinity of the substrate, and further, the source gas that has passed over the substrate is discharged along the gas flow channel and is not recirculated to the substrate again. To be considered.
そして本発明では、原料ガスを基板上に供給しながら基板の加熱温度を変更することが好ましく、このためには、たとえば、原料ガスの基板上への供給とその停止の繰り返しを、基板の加熱温度の
Ｔ1＜Ｔ2
（Ｔ1は原料ガス供給時の温度、Ｔ2は原料ガスの供給停止時の温度）
の変更と連動させることが有効でもある。
In the present invention, it is preferable to change the heating temperature of the substrate while supplying the raw material gas onto the substrate. For this purpose, for example, the supply of the raw material gas to the substrate and the repetition of the stoppage are repeated. Temperature T 1 <T 2
(T 1 is the temperature when the source gas is supplied, and T 2 is the temperature when the supply of the source gas is stopped)
It is also effective to link with changes in
Ｔ1およびＴ2については、たとえばＴ1＝３５０℃〜６００℃未満、Ｔ2＝６００℃〜９００℃のようにすることが考慮される。また、原料ガスの供給とその停止の１サイクル当りのＺｎＯ薄膜の成長は５〜５０ｎｍの範囲とすること、さらには１０〜２０ｎｍの範囲とすることが好適に考慮される。加熱手段については上記のことが実現されるように適宜に考慮されてよい。 For T 1 and T 2 , for example, it is considered that T 1 = 350 ° C. to less than 600 ° C. and T 2 = 600 ° C. to 900 ° C. In addition, the growth of the ZnO thin film per cycle of supplying and stopping the source gas is preferably set in the range of 5 to 50 nm, and more preferably in the range of 10 to 20 nm. The heating means may be appropriately considered so as to realize the above.
たとえば本発明の方法では、レーザー光を用いることが考慮される。 For example, in the method of the present invention, it is considered to use laser light.
そして、光ファイバーを用いることなしに、レーザー源からのレーザー光を直接的に基板の背面に照射して加熱する方式とすることが好ましい。この方式は、たとえば、本発明者らがすでに提案している（特願２００６−２０２６３４）真空プロセス用装置として実施可能とされるものである。この装置では、チャンバーの一部に光透過性窓が形成されており、当該光透過性窓と基板を保持する保持部とを、チャンバー内の他の箇所と隔絶した直線状空間にて繋ぎ、前記光透過性窓の外側にレーザー発進装置を配置し、レーザー発進装置から、前記直線状空間を通って前記基板にレーザー光を照射して加熱するようにしている。 And it is preferable to set it as the system which irradiates and heats the laser beam from a laser source directly to the back surface of a board | substrate, without using an optical fiber. This method can be implemented, for example, as a vacuum process apparatus that has already been proposed by the present inventors (Japanese Patent Application No. 2006-202634). In this apparatus, a light transmissive window is formed in a part of the chamber, and the light transmissive window and a holding unit that holds the substrate are connected to each other in a linear space that is isolated from other portions in the chamber. A laser starting device is disposed outside the light-transmitting window, and the substrate is heated by irradiating the substrate with laser light through the linear space from the laser starting device.
また、直線状空間は、光透過性窓の内側面と保持部とを繋ぐ筒状体にて形成することを好適な形態の一つとしてもいる。 Further, the linear space is preferably formed by a cylindrical body that connects the inner surface of the light transmissive window and the holding portion.
なお、本発明の酸化亜鉛薄膜に於ける「薄膜」の厚みについては、特に限定されるものではないが、ＺｎＯ−ＬＥＤ等の観点からは、通常は、５μｍ以下、たとえば実際的には３μｍ以下であることが考慮される。 The thickness of the “thin film” in the zinc oxide thin film of the present invention is not particularly limited. However, from the viewpoint of ZnO-LED or the like, it is usually 5 μm or less, for example, actually 3 μm or less. It is considered that.
そこで以下に実施例を示し、さらに詳しく本発明の方法について説明する。もちろん以下の例によって本発明が限定されることはない。 Then, an Example is shown below and the method of this invention is demonstrated in detail. Of course, the present invention is not limited to the following examples.
図１に示したように、真空チャンバー内に、光透過性の窓の内面と基板保持部（２）とを筒状体（３）にて直線状空間（４）として連通させ、この直線状空間（４）を通って、外部のレーザー源からのレーザー光（５）が直接的に基板（１）の背面に照射されて基板（１）が加熱されるようにした真空プロセス装置を用いる。この装置では、レーザー光（５）の通路としての直線状空間（４）には原料ガスが流入しないようになっている。そして、従来のように光ファイバーを用いることなく、レーザー光（５）を直接的に基板（１）に照射するようにしている。この装置では、レーザー光（５）は、チャンバー内の他の箇所に充満する蒸気や薄膜とは直線状空間内では接触しないので、レーザー光（５）は、減衰することなく基板（１）に至り、ＭＯＣＶＤ法等による薄膜堆積時の基板温度を短時間で変調することができ、しかも長時間安定に例えば１５００度以上の高温にも加熱することができる。 As shown in FIG. 1, the inner surface of the light-transmitting window and the substrate holding part (2) are communicated as a linear space (4) with a cylindrical body (3) in the vacuum chamber. A vacuum process apparatus is used in which the substrate (1) is heated by directly irradiating the back surface of the substrate (1) with laser light (5) from an external laser source through the space (4). In this apparatus, the raw material gas does not flow into the linear space (4) as a passage for the laser beam (5). Then, the substrate (1) is directly irradiated with the laser beam (5) without using an optical fiber as in the prior art. In this apparatus, the laser beam (5) does not come into contact with vapor or a thin film filling other portions in the chamber in a linear space, so that the laser beam (5) is not attenuated on the substrate (1). Finally, the substrate temperature during thin film deposition by MOCVD or the like can be modulated in a short time, and can be stably heated to a high temperature of, for example, 1500 ° C. or more stably for a long time.
また、図１に示したように、基板（１）上には、たとえば３ｍｍ高さのガス流通空間（６）を介して基板表面を覆うフローチャンネル（７）を配設する。このフローチャンネル（７）は、たとえばその材質をＳＵＳ３１６によるものとし、ガス流通空間（６）は一つの領域を幅３ｃｍ、高さ１ｍｍで三つの空間を区切り、それぞれの空間にそして、このフローチャンネル（７）を通じて、図１に示したように、たとえば、原料ガスであるジエチル亜鉛（ＤＥＺｎ）とキャリアー水素ガス（４００ｓｃｃｍ）と、酸素（Ｏ2）、さらに
その上層の水素（Ｈ2）ガス（３００ｓｃｃｍ）の各々が導入されるようになっている。
そして導入されたガスは、仕切りのない基板（１）直前の領域で混ざるようになっている。
Further, as shown in FIG. 1, on the substrate (1), a flow channel (7) that covers the surface of the substrate via a gas flow space (6) having a height of 3 mm, for example, is disposed. The flow channel (7) is made of, for example, SUS316, and the gas distribution space (6) is divided into three spaces each having a width of 3 cm and a height of 1 mm. Through (7), as shown in FIG. 1, for example, diethyl zinc (DEZn) as a source gas, carrier hydrogen gas (400 sccm), oxygen (O 2 ), and hydrogen (H 2 ) gas ( 300 sccm) are introduced.
The introduced gas is mixed in the region immediately before the substrate (1) without a partition.
またフローチャンネル（７）のもう一方の端部は開放されており、基板（１）上を通過した原料ガスはそのまま流れて、真空チャンバー内を真空引きしているポンプで外部に排気される。 The other end of the flow channel (7) is open, and the source gas that has passed over the substrate (1) flows as it is and is exhausted to the outside by a pump that evacuates the vacuum chamber.
このため、基板上を通過した原料ガスは再度基板まで還流することがない。以上のようなガスフロー状態において、レーザー光（５）の照射によって基板（１）を加熱することでＭＯＣＶＤによりＺｎＯ薄膜を基板（１）の表面上に成長させる。その際の原料ガスの供給量や圧力、基板温度等の条件は次の表１のとおりとする。 For this reason, the source gas that has passed over the substrate does not recirculate to the substrate again. In the gas flow state as described above, the ZnO thin film is grown on the surface of the substrate (1) by MOCVD by heating the substrate (1) by irradiation with the laser beam (5). The conditions such as the supply amount of raw material gas, pressure, and substrate temperature are as shown in Table 1 below.
なお、ａ面サファイア基板は、たとえば１０００℃真空アニール後に水素処理したものを用いる。 As the a-plane sapphire substrate, for example, a substrate subjected to hydrogen treatment after vacuum annealing at 1000 ° C. is used.
そして、以上のＭＯＣＶＤについては、図２に示したとおりのＤＥＺｎガスの間欠供給と、レーザー照射による急速加熱と冷却との連動サイクルを繰り返して行いＺｎＯ薄膜を成長させることを試みる。これによって、０．７μｍ厚程度までＺｎＯ薄膜を成長させる。 For the above MOCVD, an attempt is made to grow a ZnO thin film by repeating an interlocking cycle of intermittent supply of DEZn gas and rapid heating and cooling by laser irradiation as shown in FIG. Thereby, a ZnO thin film is grown to a thickness of about 0.7 μm.
図３は、圧力３０Ｔｏｒｒと１００Ｔｏｒｒの場合のＺｎＯ薄膜表面のＳＥＭ像であり、図４は、＜１１−２０＞方向からのＲＨＥＥＤパターンである。 FIG. 3 is an SEM image of the ZnO thin film surface at pressures of 30 Torr and 100 Torr, and FIG. 4 is an RHEED pattern from the <11-20> direction.
そして、図５は、結晶性を示す（０００２）面のロッキングカーブの半値幅の１サイク
ル当りのＺｎＯ膜厚依存性を示し、図６は、ＺｎＯ薄膜の１０Ｋで観測したフォトルミネッセンススペクトルを示している。
FIG. 5 shows the dependence of the full width at half maximum of the rocking curve on the (0002) plane showing crystallinity on the ZnO film thickness per cycle, and FIG. 6 shows the photoluminescence spectrum of the ZnO thin film observed at 10K. Yes.
これらの結果から、極めて平坦な表面の、エピタキシャルなＺｎＯ薄膜が成長していることが確認される。具体的には、表面が平坦でＲＨＥＥＤで明瞭な１次ラウエが観察できるほど良好であって、かつ、フォトルミネッセンススペクトルにおいてエキシトンのｎ＝２の発光が明瞭に観察できるほど高品質なＺｎＯ薄膜が実現される。また、１サイクル当りの膜厚が１０〜１５ｎｍ付近で最も良い結晶性を示すことも確認される。 From these results, it is confirmed that an epitaxial ZnO thin film having an extremely flat surface is grown. Specifically, a ZnO thin film having such a high quality that the surface is flat and RHEED can be clearly observed as a primary Laue, and the emission of exciton n = 2 can be clearly observed in the photoluminescence spectrum. Realized. It is also confirmed that the best crystallinity is exhibited when the film thickness per cycle is around 10 to 15 nm.
１ 基板
２ 基板保持部
３ 筒状体
４ 直線状空間
５ レーザー光
６ ガス流通空間
７ フローチャンネル
DESCRIPTION OF SYMBOLS 1 Board | substrate 2 Board | substrate holding | maintenance part 3 Cylindrical body 4 Linear space 5 Laser beam 6 Gas distribution space 7 Flow channel
Claims (5)
Ｔ１＜Ｔ２
（Ｔ１は原料ガス供給時の温度、Ｔ２は原料ガスの供給停止時の温度）の変更と連動させることを特徴とするとする請求項１または２に記載の酸化亜鉛薄膜の形成方法。 The supply of the source gas onto the substrate and the repetition of the stop are repeated by T 1 <T 2 of the substrate heating temperature.
(T 1 is the raw material gas supply when the temperature, T 2 is the temperature at the time of stopping supply of the raw material gas) method for forming a zinc oxide thin film according to claim 1 or 2, characterized in that to link and change.
The method for forming a zinc oxide thin film according to any one of claims 1 to 3 , wherein the substrate is heated by direct irradiation of laser light from a laser source.
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